A SiO2 particle was prepared with different alkali sources, and then lamellar-stacked TS-1 catalysts were hydrothermally synthesized using the SiO2 particle as a silica source. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectra, nitrogen adsorption-desorption and UV-vis absorption spectra were used to characterize the TS-1 catalysts. The effect of the alkali source during the preparation of the SiO2 particle on the textural properties and catalytic performance of the TS-1 catalyst was thoroughly investigated. The TS-1 catalyst that was prepared with a SiO2 particle using tetrapropylammonium hydroxide (TPAOH) as an alkali source (TS-1-TPAOH) possessed more meso- and macro-pores and a higher framework Ti content than the catalyst that was prepared with a SiO2 particle using NH3 center dot H2O as an alkali source (TS-1-NH3 center dot H2O). As a result, the TS-1-TPAOH catalyst had a better catalytic performance for butanone ammoximation with H2O2 than conventional TS-1 and TS-1-NH3 center dot H2O catalysts. Furthermore, the influences of reaction conditions, including reaction temperature, reaction time, the amount of catalyst and the molar ratio between H2O2 and butyl ketone oxime on the catalytic performance of the TS-1-TPAOH catalyst were evaluated. The unique structure of the lamellar-stacked TS-1 catalyst can effectively avoid the diffusing of large reactant molecules into zeolite channels and has potential applications in other oxidation reactions.